An experimental nanocalorimetric study of mass selected protonated (H2O)nH+ and deprotonated (H2O)n−1OH− water clusters is reported in the size range n = 20-118. Water cluster's heat capacities exhibit a change of slope at size dependent temperatures varying from 90 to 140 K, which is ascribed to phase or structural transition. For both anionic and cationic species, these transition temperatures strongly vary at small sizes, with higher amplitude for protonated than for deprotonated clusters, and change more smoothly above roughly n ≈ 35. There is a correlation between bonding energies and transition temperatures, which is split in two components for protonated clusters while only one component is observed for deprotonated clusters. These features are tentatively interpreted in terms of structural properties of water clusters.